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1.
Virol J ; 21(1): 70, 2024 03 21.
Artigo em Inglês | MEDLINE | ID: mdl-38515117

RESUMO

Since the emergence of SARS-CoV-2, different variants and subvariants successively emerged to dominate global virus circulation as a result of immune evasion, replication fitness or both. COVID-19 vaccines continue to be updated in response to the emergence of antigenically divergent viruses, the first being the bivalent RNA vaccines that encodes for both the Wuhan-like and Omicron BA.5 subvariant spike proteins. Repeated infections and vaccine breakthrough infections have led to complex immune landscapes in populations making it increasingly difficult to assess the intrinsic neutralizing antibody responses elicited by the vaccines. Hong Kong's intensive COVID-19 containment policy through 2020-2021 permitted us to identify sera from a small number of infection-naïve individuals who received 3 doses of the RNA BNT162b2 vaccine encoding the Wuhan-like spike (WT) and were boosted with a fourth dose of the WT vaccine or the bivalent WT and BA.4/5 spike (WT + BA.4/5). While neutralizing antibody to wild-type virus was comparable in both vaccine groups, BNT162b2 (WT + BA.4/BA.5) bivalent vaccine elicited significantly higher plaque neutralizing antibodies to Omicron subvariants BA.5, XBB.1.5, XBB.1.16, XBB.1.9.1, XBB.2.3.2, EG.5.1, HK.3, BA.2.86 and JN.1, compared to BNT162b2 monovalent vaccine. The single amino acid substitution that differentiates the spike of JN.1 from BA.2.86 resulted in a profound antigenic change.


Assuntos
Vacina BNT162 , COVID-19 , Humanos , Anticorpos Amplamente Neutralizantes , SARS-CoV-2/genética , Vacinas contra COVID-19 , COVID-19/prevenção & controle , Anticorpos Neutralizantes , Vacinação , Anticorpos Antivirais
3.
Environ Sci Technol ; 57(5): 1870-1881, 2023 02 07.
Artigo em Inglês | MEDLINE | ID: mdl-36695819

RESUMO

We report aircraft observations of extreme levels of HCl and the dihalogens Cl2, Br2, and BrCl in an industrial plume near the Great Salt Lake, Utah. Complete depletion of O3 was observed concurrently with halogen enhancements as a direct result of photochemically produced halogen radicals. Observed fluxes for Cl2, HCl, and NOx agreed with facility-reported emissions inventories. Bromine emissions are not required to be reported in the inventory, but are estimated as 173 Mg year-1 Br2 and 949 Mg year-1 BrCl, representing a major uncounted oxidant source. A zero-dimensional photochemical box model reproduced the observed O3 depletions and demonstrated that bromine radical cycling was principally responsible for the rapid O3 depletion. Inclusion of observed halogen emissions in both the box model and a 3D chemical model showed significant increases in oxidants and particulate matter (PM2.5) in the populated regions of the Great Salt Lake Basin, where winter PM2.5 is among the most severe air quality issues in the U.S. The model shows regional PM2.5 increases of 10%-25% attributable to this single industrial halogen source, demonstrating the impact of underreported industrial bromine emissions on oxidation sources and air quality within a major urban area of the western U.S.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Perda de Ozônio , Ozônio , Poluentes Atmosféricos/análise , Halogênios , Ozônio/análise , Bromo , Lagos , Poluição do Ar/análise , Material Particulado/análise , Oxidantes
4.
Geophys Res Lett ; 49(11): e2021GL097366, 2022 Jun 16.
Artigo em Inglês | MEDLINE | ID: mdl-35859850

RESUMO

Oxidation of isoprene by nitrate radicals (NO3) or by hydroxyl radicals (OH) under high NOx conditions forms a substantial amount of organonitrates (ONs). ONs impact NOx concentrations and consequently ozone formation while also contributing to secondary organic aerosol. Here we show that the ONs with the chemical formula C4H7NO5 are a significant fraction of isoprene-derived ONs, based on chamber experiments and ambient measurements from different sites around the globe. From chamber experiments we found that C4H7NO5 isomers contribute 5%-17% of all measured ONs formed during nighttime and constitute more than 40% of the measured ONs after further daytime oxidation. In ambient measurements C4H7NO5 isomers usually dominate both nighttime and daytime, implying a long residence time compared to C5 ONs which are removed more rapidly. We propose potential nighttime sources and secondary formation pathways, and test them using a box model with an updated isoprene oxidation scheme.

5.
Ann Clin Biochem ; 58(6): 593-598, 2021 11.
Artigo em Inglês | MEDLINE | ID: mdl-34167322

RESUMO

BACKGROUND: Repeated phlebotomy for laboratory diagnostic testing is a known cause of iatrogenic anaemia and in critically ill neonates often leads to blood transfusion being required. This study has developed a spreadsheet clinical decision support tool to allow neonatal staff to determine the true minimum blood volume required to analyse groups of blood tests and modelled its potential benefit compared with the existing system in use. METHODS: The tool calculates the minimum blood volume accounting for novel factors including the current patient haematocrit for plasma/serum samples, instrument minimum test and dead volumes (including those where shared) and sharing of samples within/between laboratory departments. A year of neonatal unit laboratory requests were examined comparing the volumes and containers of blood recommended by the hospital information system with both the amount actually collected by staff and that recommended by the tool. RESULTS: A total of 463 patients had 8481 blood draws for 23,899 tests or test profiles over the year. The hospital information system recommended collecting 11,222 mL of blood into 18,509 containers, while 17,734 containers were actually received (10,717 mL if fully filled). The tool recommended collecting 4915 mL of blood into 15,549 containers. CONCLUSIONS: This tool allows neonatal intensive care unit staff to objectively determine the minimum blood volume required for a combination of tests and is generalizable between laboratory instruments. Compared with the hospital information system, use of the minimum blood volume clinical decision support tool could maximally reduce the volume of blood collected from this neonatal unit by more than a half. Neonatal intensive care unit staff had apparently already gone some way to determining their own minimum volumes required.


Assuntos
Anemia , Flebotomia , Transfusão de Sangue , Estado Terminal , Testes Diagnósticos de Rotina , Humanos , Recém-Nascido
6.
Proc Natl Acad Sci U S A ; 117(47): 29469-29477, 2020 11 24.
Artigo em Inglês | MEDLINE | ID: mdl-33148807

RESUMO

The evolution of organic aerosol (OA) and brown carbon (BrC) in wildfire plumes, including the relative contributions of primary versus secondary sources, has been uncertain in part because of limited knowledge of the precursor emissions and the chemical environment of smoke plumes. We made airborne measurements of a suite of reactive trace gases, particle composition, and optical properties in fresh western US wildfire smoke in July through August 2018. We use these observations to quantify primary versus secondary sources of biomass-burning OA (BBPOA versus BBSOA) and BrC in wildfire plumes. When a daytime wildfire plume dilutes by a factor of 5 to 10, we estimate that up to one-third of the primary OA has evaporated and subsequently reacted to form BBSOA with near unit yield. The reactions of measured BBSOA precursors contribute only 13 ± 3% of the total BBSOA source, with evaporated BBPOA comprising the rest. We find that oxidation of phenolic compounds contributes the majority of BBSOA from emitted vapors. The corresponding particulate nitrophenolic compounds are estimated to explain 29 ± 15% of average BrC light absorption at 405 nm (BrC Abs405) measured in the first few hours of plume evolution, despite accounting for just 4 ± 2% of average OA mass. These measurements provide quantitative constraints on the role of dilution-driven evaporation of OA and subsequent radical-driven oxidation on the fate of biomass-burning OA and BrC in daytime wildfire plumes and point to the need to understand how processing of nighttime emissions differs.


Assuntos
Poluentes Atmosféricos/química , Carbono/análise , Fumaça , Incêndios Florestais , Aerossóis , Monitoramento Ambiental , Material Particulado , Estados Unidos
7.
Acc Chem Res ; 53(8): 1415-1426, 2020 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-32648739

RESUMO

ConspectusThe complex array of sources and transformations of organic carbonaceous material that comprises an important fraction of atmospheric fine particle mass, known as organic aerosol, has presented a long running challenge for accurate predictions of its abundance, distribution, and sensitivity to anthropogenic activities. Uncertainties about changes in atmospheric aerosol particle sources and abundance over time translate to uncertainties in their impact on Earth's climate and their response to changes in air quality policy. One limitation in our understanding of organic aerosol has been a lack of comprehensive measurements of its molecular composition and volatility, which can elucidate sources and processes affecting its abundance. Herein we describe advances in the development and application of the Filter Inlet for Gases and Aerosols (FIGAERO) coupled to field-deployable High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometers (HRToF-CIMS). The FIGAERO HRToFCIMS combination broadly probes gas and particulate OA molecular composition by using programmed thermal desorption of particles collected on a Teflon filter with subsequent detection and speciation of desorbed vapors using inherently quantitative selected-ion chemical ionization. The thermal desorption provides a means to obtain quantitative insights into the volatility of particle components and thus the physicochemical nature of the organic material that will govern its evolution in the atmosphere.In this Account, we discuss the design and operation of the FIGAERO, when coupled to the HRToF-CIMS, for quantitative characterization of the molecular-level composition and effective volatility of organic aerosol in the laboratory and field. We provide example insights gleaned from its deployment, which improve our understanding of organic aerosol sources and evolution. Specifically, we connect thermal desorption profiles to the effective equilibrium saturation vapor concentration and enthalpy of vaporization of detected components. We also show how application of the FIGAERO HRToF-CIMS to environmental simulation chamber experiments and the field provide new insights and constraints on the chemical mechanisms governing secondary organic aerosol formation and dynamic evolution. We discuss the associated challenges of thermal decomposition during desorption and calibration of both the volatility axis and signal. We also illustrate how the FIGAERO HRToF-CIMS can provide additional insights into organic aerosol through isothermal evaporation experiments as well as for detection of ultrafine particulate composition. We conclude with a description of future opportunities and needs for its ability to further organic aerosol science.

8.
ACS Earth Space Chem ; 4(3): 391-402, 2020 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-32328536

RESUMO

Organic aerosol (OA) constitutes a significant fraction of atmospheric fine particle mass. However, the precursors and chemical processes responsible for a majority of OA are rarely conclusively identified. We use online observations of hundreds of simultaneously measured molecular components obtained from 15 laboratory OA formation experiments with constraints on their effective saturation vapor concentrations to attribute the VOC precursors and subsequent chemical pathways giving rise to the vast majority of OA mass measured in two forested regions. We find that precursors and chemical pathways regulating OA composition and volatility are dynamic over hours to days, with their variations driven by coupled interactions between multiple oxidants. The extent of physical and photochemical aging, and its modulation by NOx, were key to a uniquely comprehensive combined composition-volatility description of OA. Our findings thus provide some of the most complete mechanistic-level guidance to the development of OA descriptions in air quality and Earth system models.

9.
Environ Sci Technol ; 54(10): 5954-5963, 2020 05 19.
Artigo em Inglês | MEDLINE | ID: mdl-32294377

RESUMO

Wildfires are an important source of nitrous acid (HONO), a photolabile radical precursor, yet in situ measurements and quantification of primary HONO emissions from open wildfires have been scarce. We present airborne observations of HONO within wildfire plumes sampled during the Western Wildfire Experiment for Cloud chemistry, Aerosol absorption and Nitrogen (WE-CAN) campaign. ΔHONO/ΔCO close to the fire locations ranged from 0.7 to 17 pptv ppbv-1 using a maximum enhancement method, with the median similar to previous observations of temperate forest fire plumes. Measured HONO to NOx enhancement ratios were generally factors of 2, or higher, at early plume ages than previous studies. Enhancement ratios scale with modified combustion efficiency and certain nitrogenous trace gases, which may be useful to estimate HONO release when HONO observations are lacking or plumes have photochemical exposures exceeding an hour as emitted HONO is rapidly photolyzed. We find that HONO photolysis is the dominant contributor to hydrogen oxide radicals (HOx = OH + HO2) in early stage (<3 h) wildfire plume evolution. These results highlight the role of HONO as a major component of reactive nitrogen emissions from wildfires and the main driver of initial photochemical oxidation.


Assuntos
Poluentes Atmosféricos/análise , Incêndios Florestais , Aerossóis , Ácido Nitroso/análise , Fumaça
10.
Environ Sci Technol ; 54(7): 3861-3870, 2020 04 07.
Artigo em Inglês | MEDLINE | ID: mdl-32154714

RESUMO

Secondary organic aerosol (SOA) accounts for a large fraction of the tropospheric particulate matter. Although SOA production rates and mechanisms have been extensively investigated, loss pathways remain uncertain. Most large-scale chemistry and transport models account for mechanical deposition of SOA but not chemical losses such as photolysis. There is also a paucity of laboratory measurements of SOA photolysis, which limits how well photolytic losses can be modeled. Here, we show, through a combined experimental and modeling approach, that photolytic loss of SOA mass significantly alters SOA budget predictions. Using environmental chamber experiments at variable relative humidity between 0 and 60%, we find that SOA produced from several biogenic volatile organic compounds undergoes photolysis-induced mass loss at rates between 0 and 2.2 ± 0.4% of nitrogen dioxide (NO2) photolysis, equivalent to average atmospheric lifetimes as short as 10 h. We incorporate our photolysis rates into a regional chemical transport model to test the sensitivity of predicted SOA mass concentrations to photolytic losses. The addition of photolysis causes a ∼50% reduction in biogenic SOA loadings over the Amazon, indicating that photolysis exerts a substantial control over the atmospheric SOA lifetime, with a likely dependence upon the SOA molecular composition and thus production mechanisms.


Assuntos
Poluentes Atmosféricos , Compostos Orgânicos Voláteis , Aerossóis , Modelos Químicos , Material Particulado , Fotólise
11.
Proc Natl Acad Sci U S A ; 116(14): 6641-6646, 2019 04 02.
Artigo em Inglês | MEDLINE | ID: mdl-30886090

RESUMO

Atmospheric oxidation of natural and anthropogenic volatile organic compounds (VOCs) leads to secondary organic aerosol (SOA), which constitutes a major and often dominant component of atmospheric fine particulate matter (PM2.5). Recent work demonstrates that rapid autoxidation of organic peroxy radicals (RO2) formed during VOC oxidation results in highly oxygenated organic molecules (HOM) that efficiently form SOA. As NOx emissions decrease, the chemical regime of the atmosphere changes to one in which RO2 autoxidation becomes increasingly important, potentially increasing PM2.5, while oxidant availability driving RO2 formation rates simultaneously declines, possibly slowing regional PM2.5 formation. Using a suite of in situ aircraft observations and laboratory studies of HOM, together with a detailed molecular mechanism, we show that although autoxidation in an archetypal biogenic VOC system becomes more competitive as NOx decreases, absolute HOM production rates decrease due to oxidant reductions, leading to an overall positive coupling between anthropogenic NOx and localized biogenic SOA from autoxidation. This effect is observed in the Atlanta, Georgia, urban plume where HOM is enhanced in the presence of elevated NO, and predictions for Guangzhou, China, where increasing HOM-RO2 production coincides with increases in NO from 1990 to 2010. These results suggest added benefits to PM2.5 abatement strategies come with NOx emission reductions and have implications for aerosol-climate interactions due to changes in global SOA resulting from NOx interactions since the preindustrial era.

12.
Proc Natl Acad Sci U S A ; 115(32): 8110-8115, 2018 08 07.
Artigo em Inglês | MEDLINE | ID: mdl-30037992

RESUMO

Sulfate ([Formula: see text]) and nitrate ([Formula: see text]) account for half of the fine particulate matter mass over the eastern United States. Their wintertime concentrations have changed little in the past decade despite considerable precursor emissions reductions. The reasons for this have remained unclear because detailed observations to constrain the wintertime gas-particle chemical system have been lacking. We use extensive airborne observations over the eastern United States from the 2015 Wintertime Investigation of Transport, Emissions, and Reactivity (WINTER) campaign; ground-based observations; and the GEOS-Chem chemical transport model to determine the controls on winter [Formula: see text] and [Formula: see text] GEOS-Chem reproduces observed [Formula: see text]-[Formula: see text]-[Formula: see text] particulate concentrations (2.45 µg [Formula: see text]) and composition ([Formula: see text]: 47%; [Formula: see text]: 32%; [Formula: see text]: 21%) during WINTER. Only 18% of [Formula: see text] emissions were regionally oxidized to [Formula: see text] during WINTER, limited by low [H2O2] and [OH]. Relatively acidic fine particulates (pH∼1.3) allow 45% of nitrate to partition to the particle phase. Using GEOS-Chem, we examine the impact of the 58% decrease in winter [Formula: see text] emissions from 2007 to 2015 and find that the H2O2 limitation on [Formula: see text] oxidation weakened, which increased the fraction of [Formula: see text] emissions oxidizing to [Formula: see text] Simultaneously, NOx emissions decreased by 35%, but the modeled [Formula: see text] particle fraction increased as fine particle acidity decreased. These feedbacks resulted in a 40% decrease of modeled [[Formula: see text]] and no change in [[Formula: see text]], as observed. Wintertime [[Formula: see text]] and [[Formula: see text]] are expected to change slowly between 2015 and 2023, unless [Formula: see text] and NOx emissions decrease faster in the future than in the recent past.

13.
Int J Clin Pharm ; 40(4): 803-805, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-29855987

RESUMO

The use of antiandrogen drugs such as finasteride during pregnancy may carry the risk of birth defects, especially hypospadias. We report a 39-year-old woman, with 5 weeks unplanned pregnancy, the patient conceived while receiving daily dose of finasteride 2.5 mg for treatment of alopecia. The patient's partner was concurrently using finasteride for the same purpose. Ultrasound scans including detailed anatomy were normal throughout pregnancy and the fetal gender was detected to be male. The patient had her delivery at 38+5 weeks' gestation, by elective cesarean section, a male infant with a weight of 3.58 kg and Apgar score of 9 and 10 at 1 and 5-min, respectively. The infant was healthy with no obvious dysmorphic features. In this case report, maternal use of finasteride in early pregnancy was not associated with external genitalia abnormalities of a male baby. Moreover, maternal exposure to the semen of partner who received finasteride did not adversely affect the short term neonatal outcomes. However, absence of apparent neonatal adverse effects in a single case report does not indicate safety of use. Population-based long term neonatal outcomes are yet to be established.


Assuntos
Inibidores de 5-alfa Redutase/administração & dosagem , Alopecia/tratamento farmacológico , Finasterida/administração & dosagem , Gravidez não Planejada , Inibidores de 5-alfa Redutase/efeitos adversos , Anormalidades Induzidas por Medicamentos/etiologia , Adulto , Cesárea , Esquema de Medicação , Procedimentos Cirúrgicos Eletivos , Feminino , Finasterida/efeitos adversos , Idade Gestacional , Humanos , Recém-Nascido , Nascido Vivo , Masculino , Exposição Materna/efeitos adversos , Exposição Paterna/efeitos adversos , Gravidez , Efeitos Tardios da Exposição Pré-Natal , Medição de Risco , Fatores de Risco
14.
Proc Natl Acad Sci U S A ; 115(9): 2038-2043, 2018 02 27.
Artigo em Inglês | MEDLINE | ID: mdl-29440409

RESUMO

The chemical complexity of atmospheric organic aerosol (OA) has caused substantial uncertainties in understanding its origins and environmental impacts. Here, we provide constraints on OA origins through compositional characterization with molecular-level details. Our results suggest that secondary OA (SOA) from monoterpene oxidation accounts for approximately half of summertime fine OA in Centreville, AL, a forested area in the southeastern United States influenced by anthropogenic pollution. We find that different chemical processes involving nitrogen oxides, during days and nights, play a central role in determining the mass of monoterpene SOA produced. These findings elucidate the strong anthropogenic-biogenic interaction affecting ambient aerosol in the southeastern United States and point out the importance of reducing anthropogenic emissions, especially under a changing climate, where biogenic emissions will likely keep increasing.


Assuntos
Aerossóis/química , Poluentes Atmosféricos/química , Monoterpenos/química , Estações do Ano , Sudeste dos Estados Unidos , Fatores de Tempo
15.
J Geophys Res Atmos ; 123(19): 11225-11237, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30997299

RESUMO

We present airborne observations of gaseous reactive halogen species (HCl, Cl2, ClNO2, Br2,BrNO2, and BrCl), sulfur dioxide (SO2), and nonrefractory fine particulate chloride (pCl) and sulfate(pSO4) in power plant exhaust. Measurements were conducted during the Wintertime INvestigation of Transport, Emissions, and Reactivity campaign in February-March of 2015 aboard the NCAR-NSF C-130 aircraft. Fifty air mass encounters were identified in which SO2 levels were elevated ~5 ppb above ambient background levels and in proximity to operational power plants. Each encounter was attributed to one or more potential emission sources using a simple wind trajectory analysis. In case studies, we compare measured emission ratios to those reported in the 2011 National Emissions Inventory and present evidence of the conversion of HCl emitted from power plants to ClNO2. Taking into account possible chemical conversion downwind, there was general agreement between the observed and reported HCl: SO2 emission ratios. Reactive bromine species (Br2, BrNO2, and/or BrCl) were detected in the exhaust of some coal-fired power plants, likely related to the absence of wet flue gas desulfurization emission control technology. Levels of bromine species enhanced in some encounters exceeded those expected assuming all of the native bromide in coal was released to the atmosphere, though there was no reported use of bromide salts (as a way to reduce mercury emissions) during Wintertime INvestigation of Transport, Emissions, and Reactivity observations. These measurements represent the first ever in-flight observations of reactive gaseous chlorine and bromine containing compounds present in coal-fired power plant exhaust.

16.
J Pediatr Orthop ; 37(1): 23-29, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-26134078

RESUMO

BACKGROUND: There is growing concern over the relationship between the severity of pediatric fractures and low vitamin D [25-hydroxyvitaminD (25(OH)D)] status. OBJECTIVE: Compare 25(OH)D levels and lifestyle of children with fractures to nonfracture controls to determine if 25(OH)D levels are associated with fractures and if there is a 25(OH)D fragility fracture threshold. METHODS: Pediatric fracture and nonfracture controls were included. Bone health survey and medical record data were analyzed. Fractures were categorized using the Abbreviated Injury Scale (AIS). AIS 3 fractures were identified as fractures that required surgical intervention. Univariate and multivariable ordinal regression analyses were performed to identify potential risk factors for increased fracture severity. RESULTS: A total of 369 fracture patients and 662 nonfracture controls aged 18 years and younger were included. Both groups' 25(OH)D levels were comparable. 25(OH)D was 27.5±8.9 in the fracture group compared with 27.4±9.1 ng/mL in nonfracture controls (P=0.914). AIS 3 fractures had lower 25(OH)D levels (24.6±9.3 ng/mL) versus AIS 1 and 2 (30.0±10.8 and 28.3±8.4, respectively, P=0.001). Univariate correlations for AIS severity were found with age (P=0.015) and outdoor playtime (P=0.042). Adjusted odds ratios for 25(OH)D levels <12 ng/mL was 55.4 (P=0.037), 25(OH)D between 12 and 20 ng/mL was 6.7 (P=0.039), 25(OH)D between 20 and 30 ng/mL was 2.8 (P=0.208), and 25(OH)D between 30 and 40 was 1.7 (P=0.518). CLINICAL RELEVANCE: Occurrence of a pediatric fracture was not associated with 25(OH)D levels in our study. However, children with lower vitamin D levels were found to be at higher risk for more severe fractures. Early evidence suggests that the target serum level for 25(OH)D should be at least 40 ng/mL in patients less than 18 years of age as the relative risk of more severe fractures increased as 25(OH)D levels decreased <40 ng/mL. LEVEL OF EVIDENCE: Level III.


Assuntos
Fraturas Ósseas/epidemiologia , Deficiência de Vitamina D/epidemiologia , Vitamina D/análogos & derivados , Escala Resumida de Ferimentos , Adolescente , Estudos de Casos e Controles , Criança , Pré-Escolar , Feminino , Fraturas Ósseas/sangue , Humanos , Masculino , Análise Multivariada , Análise de Regressão , Fatores de Risco , Vitamina D/sangue , Deficiência de Vitamina D/sangue
17.
Atmos Chem Phys ; 17(3): 2103-2162, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-30147712

RESUMO

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

18.
Environ Sci Technol ; 50(18): 9872-80, 2016 09 20.
Artigo em Inglês | MEDLINE | ID: mdl-27548285

RESUMO

With a large global emission rate and high reactivity, isoprene has a profound effect upon atmospheric chemistry and composition. The atmospheric pathways by which isoprene converts to secondary organic aerosol (SOA) and how anthropogenic pollutants such as nitrogen oxides and sulfur affect this process are subjects of intense research because particles affect Earth's climate and local air quality. In the absence of both nitrogen oxides and reactive aqueous seed particles, we measure SOA mass yields from isoprene photochemical oxidation of up to 15%, which are factors of 2 or more higher than those typically used in coupled chemistry climate models. SOA yield is initially constant with the addition of increasing amounts of nitric oxide (NO) but then sharply decreases for input concentrations above 50 ppbv. Online measurements of aerosol molecular composition show that the fate of second-generation RO2 radicals is key to understanding the efficient SOA formation and the NOx-dependent yields described here and in the literature. These insights allow for improved quantitative estimates of SOA formation in the preindustrial atmosphere and in biogenic-rich regions with limited anthropogenic impacts and suggest that a more-complex representation of NOx-dependent SOA yields may be important in models.


Assuntos
Aerossóis , Atmosfera/química , Poluentes Atmosféricos , Óxido Nítrico/química , Óxidos de Nitrogênio , Oxirredução
20.
Proc Natl Acad Sci U S A ; 113(6): 1516-21, 2016 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-26811465

RESUMO

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas-particle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.

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